JPH02279654A - Production of methacrylic acid ester - Google Patents
Production of methacrylic acid esterInfo
- Publication number
- JPH02279654A JPH02279654A JP10016789A JP10016789A JPH02279654A JP H02279654 A JPH02279654 A JP H02279654A JP 10016789 A JP10016789 A JP 10016789A JP 10016789 A JP10016789 A JP 10016789A JP H02279654 A JPH02279654 A JP H02279654A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- alcohol
- separation column
- reactor
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000005397 methacrylic acid ester group Chemical group 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 7
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 43
- 238000000926 separation method Methods 0.000 claims description 38
- 230000032050 esterification Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 abstract description 2
- 229920002125 Sokalan® Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- -1 propatool Chemical compound 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はメタクリル酸エステルの製造方法に関する。更
に詳しく述べると、メタクリル酸と、炭素数１〜４の低
級脂肪族アルコールまたは脂環式アルコールとをエステ
ル化反応させることからなるメタクリル酸エステルの製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing methacrylic acid ester. More specifically, the present invention relates to a method for producing methacrylic acid ester, which comprises esterifying methacrylic acid and a lower aliphatic alcohol or alicyclic alcohol having 1 to 4 carbon atoms.
［従来の技術］
従来、メタクリル酸エステルを連続的に製造するに際し
て、メタクリル酸とアルコールとを反応器にて硫酸、リ
ン酸等の鉱酸や強酸性陽イオン交換樹脂のエステル化触
媒を用いて反応させ、メタクリル酸分離塔にて反応生成
物を蒸留して未反応のメタクリル酸を主成分とする高沸
点分と生成メタクリル酸エステル、未反応アルコールお
よび生成水を主成分とする低沸点分とに分離し、更に、
前者からはメタクリル酸を適宜精製処理して反応原料と
ともに循環再使用する一方、後者からはメタクリル酸エ
ステルを分離・精製するとともに未反応アルコールを回
収して反応器へ循環す・る操作が行なわれている（特公
昭６２−１５５４２号、特公昭６１−４３７８号、特開
昭５８−１５９４４２号各公報）。[Prior art] Conventionally, when producing methacrylic acid ester continuously, methacrylic acid and alcohol are mixed in a reactor using mineral acids such as sulfuric acid or phosphoric acid or an esterification catalyst such as a strongly acidic cation exchange resin. The reaction product is distilled in a methacrylic acid separation column to separate a high boiling point component mainly consisting of unreacted methacrylic acid and a low boiling point component mainly consisting of the produced methacrylic acid ester, unreacted alcohol and produced water. Separated into
From the former, methacrylic acid is appropriately purified and recycled together with the reaction raw materials, while from the latter, methacrylic acid ester is separated and purified, and unreacted alcohol is recovered and recycled to the reactor. (Japanese Patent Publications No. 62-15542, Japanese Patent Publication No. 61-4378, and Japanese Patent Application Laid-Open No. 58-159442).
硫酸、リン酸等の鉱酸をエステル化触媒として用いる方
法（特公昭６２−１５５４２号）では、触媒を連続的に
反応器に投入するため触媒の経時劣化がなく反応系内の
状態を一定に保つ利点があるが、腐食性の高い鉱酸を用
いるので耐食性の機器材質を選定せざるをえず、機器が
高価になると同時に、廃液中に含まれる鉱酸を無害化す
る廃液処理も繁雑となる欠点を有する。In the method of using mineral acids such as sulfuric acid and phosphoric acid as esterification catalysts (Japanese Patent Publication No. 15542/1986), the catalyst is continuously introduced into the reactor, so the catalyst does not deteriorate over time and the conditions in the reaction system are kept constant. However, since highly corrosive mineral acids are used, corrosion-resistant equipment materials must be selected, which makes the equipment expensive and requires complicated wastewater treatment to render the mineral acids contained in the wastewater harmless. It has some drawbacks.
一方、強酸性陽イオン交換樹脂をエステル化触媒として
用いる方法（特公昭６２−１５５４２号、特公昭６１−
４３７８号、特開昭５８−１５９４４２号各公報）では
上述の鉱酸をエステル化触媒として用いる方法のような
欠点は起こらない。しかし、エステル化触媒として反応
器に充填きれた強酸性陽イオン交換樹脂は長期にわたっ
て交換されることがなく、連続運転に伴って経時的に樹
脂の劣化が起こる。また、エステル化反応後、反応生成
物はメタクリル酸分離塔にて蒸留するが、該メタクリル
酸分離塔においては、高温になると重合物の生成が顕著
になったり急激な重合の危険が生じるので許容できる塔
底温度の上限を規定してこの規定温度以下に納まるよう
に完全にメタクリル酸を分離せずにメタクリル酸エステ
ルを含んだ状態で塔底液を抜き出し、適宜精製処理して
反応原料とともに循環再使用することが行なわれている
。ところが、転化率の低下によって、メタクリル酸エス
テル収量を確保するためにはメタクリル酸分離塔の塔底
液中のメタクリル酸エステルの組成を低下させねばなら
ず、メタクリル酸分離塔塔底温度が上昇してくる。その
結果、重合物の生成が増えて収率低下し、ついには規定
した温度に到達したところで運転を停止して触媒交換が
行なわれる。更には、メタクリル酸分離塔の塔底液は反
応器に循環されるので塔底液組成が変化するのに伴って
反応器入口での液組成も変化し、樹脂がＷ潤または収縮
を起こし場合によっては割れが起こったりし、このこと
もまた樹脂寿命を短くする要因となっている。On the other hand, a method using a strongly acidic cation exchange resin as an esterification catalyst (Japanese Patent Publication No. 15542/1983, Japanese Patent Publication No. 61/1983)
No. 4378 and Japanese Unexamined Patent Publication No. 159442/1983), the disadvantages of the above-mentioned method using a mineral acid as an esterification catalyst do not occur. However, the strongly acidic cation exchange resin filled in the reactor as an esterification catalyst is not replaced for a long period of time, and the resin deteriorates over time due to continuous operation. In addition, after the esterification reaction, the reaction product is distilled in a methacrylic acid separation column, but in the methacrylic acid separation column, when the temperature reaches high temperatures, the formation of polymers becomes noticeable and there is a risk of rapid polymerization, so this is not acceptable. The upper limit of the bottom temperature that can be produced is defined, and in order to keep it below this specified temperature, the bottom liquid is extracted while containing methacrylic acid ester without completely separating the methacrylic acid, and is purified as appropriate and recycled together with the reaction raw materials. It is being reused. However, due to the decrease in conversion rate, the composition of methacrylic acid ester in the bottom liquid of the methacrylic acid separation column must be lowered in order to ensure the methacrylic acid ester yield, and the bottom temperature of the methacrylic acid separation column increases. It's coming. As a result, the production of polymers increases and the yield decreases, and when the specified temperature is finally reached, the operation is stopped and the catalyst is replaced. Furthermore, since the bottom liquid of the methacrylic acid separation tower is circulated to the reactor, as the bottom liquid composition changes, the liquid composition at the reactor inlet also changes, and the resin may become wet or shrink. In some cases, cracks may occur, which is also a factor in shortening the life of the resin.
［発明が解決しようとする課題］
本発明の目的はこのような従来法の欠点を改善すること
にある。即ち安価な機器材質を、用い、廃液処理費用を
削減し、長期間の連続運転が可能になるよ）に樹脂寿命
を維持するメタクリル酸エステルの製造方法を提供する
ことにある。[Problems to be Solved by the Invention] An object of the present invention is to improve the drawbacks of such conventional methods. That is, the object of the present invention is to provide a method for producing methacrylic acid ester that uses inexpensive equipment materials, reduces waste liquid treatment costs, and maintains the life of the resin (which enables long-term continuous operation).
［課題を解決す名ための手段］
本発明者等は鋭意検討の結果、メタクリル酸と炭素数１
〜４の低級脂肪族アルコールまたは脂環式アルコールを
強酸性陽イオン交換樹脂を触媒としてエステル化反応さ
せる際に、メタクリル酸の転化率が常に一定になる様に
反応温度を調節しながらエステル化反応させることによ
って、メタクリル酸分離塔を安定した状態で運転でき、
エステル化反応器に循環する循環液の組成が安定し、反
応器の入口液組成も安定し、前記本発明の目的を速成で
きることを見出した。即ち本発明はメタクリル酸と、炭
素数１〜４の低級脂肪族アルコールまたは脂環式アルコ
ールとをエステル化反応器に供給し、該反応器にて強酸
性陽イオン交換樹脂を触媒としてメタクリル酸の転化率
が常に一定になる様に反応温度を調節しながらエステル
化反応させ、得られた反応生成物をメタクリル酸分離塔
に導いて、メタクリル酸分離塔の塔頂からメタクリル酸
エステル、水および未反応アルコールを留去させる一方
、メタクリル酸分離塔の塔底から実質的に全量のメタク
リル酸を含む液を抜きだして循環液としてエステル化反
応器に循環させることを特徴とするメタクリル酸エステ
ルの製造方法である。以下に本発明を更に詳しく説明す
る。[Means for solving the problem] As a result of intensive studies, the present inventors found that methacrylic acid and
When the lower aliphatic alcohol or alicyclic alcohol of ~4 is esterified using a strongly acidic cation exchange resin as a catalyst, the esterification reaction is carried out while adjusting the reaction temperature so that the conversion rate of methacrylic acid is always constant. By doing so, the methacrylic acid separation tower can be operated in a stable condition,
It has been found that the composition of the circulating liquid circulating in the esterification reactor is stabilized, and the composition of the inlet liquid of the reactor is also stabilized, so that the object of the present invention can be achieved quickly. That is, in the present invention, methacrylic acid and a lower aliphatic alcohol or alicyclic alcohol having 1 to 4 carbon atoms are supplied to an esterification reactor, and in the reactor, methacrylic acid is catalyzed using a strongly acidic cation exchange resin. The esterification reaction is carried out while adjusting the reaction temperature so that the conversion rate is always constant.The obtained reaction product is led to a methacrylic acid separation column, and from the top of the methacrylic acid separation column, methacrylic acid ester, water and unsaturated ester are separated. Production of methacrylic acid ester, characterized in that while distilling off the reaction alcohol, a liquid containing substantially the entire amount of methacrylic acid is extracted from the bottom of a methacrylic acid separation column and circulated as a circulating liquid to an esterification reactor. It's a method. The present invention will be explained in more detail below.
本発明で使用するメタクリル酸は粗製メタクリル酸及び
精製メタクリル酸のいずれも使用可能であり、エステル
化反応後、メタクリル酸分離塔から回収される未反応メ
タクリル酸も循環再使用される。The methacrylic acid used in the present invention can be either crude methacrylic acid or purified methacrylic acid, and unreacted methacrylic acid recovered from the methacrylic acid separation column after the esterification reaction is also recycled and reused.
炭素数１〜４の低級の脂肪族アルコールまたは脂環式ア
ルコールの具体例としてはメタノール。A specific example of the lower aliphatic alcohol or alicyclic alcohol having 1 to 4 carbon atoms is methanol.
エタノール、プロパツール、ブタノール等が挙げられ、
これらは直鎖状のものであっても分岐を有するものであ
っても良い。また、エステル化反応後、メタクリル酸エ
ステルを精製する過程で回収される未反応アルコールを
循環再使用してもよい。Examples include ethanol, propatool, butanol, etc.
These may be linear or branched. Furthermore, after the esterification reaction, unreacted alcohol recovered during the process of purifying the methacrylic acid ester may be recycled and reused.
本発明ではエステル化反応用の触媒として強酸性陽イオ
ン交換樹脂を用いる。多孔質またはゲルタイプの樹脂が
使用可能であるが多孔質タイプの樹脂が好適に用いられ
る。特に粗製メタクリル酸を使用する場合には耐有機汚
染性に優れた多孔質タイプの樹脂を使用するのが好まし
い。多孔質の強酸性陽イオン交換樹脂としては架橋度２
〜１６％、ポロシティ０． １〜１． Ｏｎ＋ｌ／ｇ
、 平均細孔径１００〜６００人のものが好ましく使
用でき、具体例としてはＣ−２６Ｃ（デュオライト社製
）。In the present invention, a strongly acidic cation exchange resin is used as a catalyst for the esterification reaction. Although porous or gel type resins can be used, porous type resins are preferably used. Particularly when crude methacrylic acid is used, it is preferable to use a porous type resin that has excellent resistance to organic staining. As a porous strongly acidic cation exchange resin, the degree of crosslinking is 2.
~16%, porosity 0. 1-1. On+l/g
, those having an average pore diameter of 100 to 600 are preferably used, and a specific example is C-26C (manufactured by Duolite).
ＰＫ−２０８，ＰＫ−２１６，ＰＫ−２２８（三菱化成
社製）、ＭＳＣ−１，８８（ダウ社製）。PK-208, PK-216, PK-228 (manufactured by Mitsubishi Chemical Corporation), MSC-1,88 (manufactured by Dow Corporation).
アンバーリスト−１６（ローム アンド ハース社製）
、５ＰＣ−１０８，５ＰＣ−１１２（バイエル社製）な
どが挙げられる。Amberlyst-16 (manufactured by Rohm and Haas)
, 5PC-108, 5PC-112 (manufactured by Bayer), and the like.
エステル化反応は反応器入口液、出口液の組成を分析す
るなどしてメタクリル酸の転化率を監視し、該転化率が
常に一定になる様に反応温度を調節しながら行なわれる
。好ましくは運転を開始して定常状態に達したときのメ
タクリル酸の転化率を基準として、±５％以内、より好
ましくは±３％以内の範囲に納まる転化率とする。また
、高い選択率を得るためにメタクリル酸の転化率は１５
〜５０％の範囲であるのが好ましい。この場合、反応温
度を調節しても、転化率は一定であって選択率も高いた
めに反応器出口の液組成があまり変化せずに安定した運
転条件が保たれる。The esterification reaction is carried out by monitoring the conversion rate of methacrylic acid by analyzing the composition of the reactor inlet liquid and outlet liquid, and adjusting the reaction temperature so that the conversion rate is always constant. Preferably, the conversion rate is within ±5%, more preferably within ±3%, based on the conversion rate of methacrylic acid when a steady state is reached after starting the operation. In addition, in order to obtain high selectivity, the conversion rate of methacrylic acid is 15
The range is preferably 50%. In this case, even if the reaction temperature is adjusted, the conversion rate remains constant and the selectivity is high, so that the liquid composition at the reactor outlet does not change much and stable operating conditions are maintained.
運転開始から触媒を寿命として交換するまでの反応温度
範囲は目的とするエステル化反応によって異なるが、通
常５０〜１１０℃である。また、エステル化反応は液相
にて行なわ札 反応型式としては流動床、固定床いずれ
でもよく、複数の反応器を順次切り換えて触媒交換しつ
つ連続操業することも可能である。The reaction temperature range from the start of operation until the catalyst reaches the end of its service life and is replaced varies depending on the intended esterification reaction, but is usually 50 to 110°C. Furthermore, the esterification reaction is carried out in a liquid phase.The reaction type may be either a fluidized bed or a fixed bed, and it is also possible to operate continuously by sequentially switching over a plurality of reactors and exchanging the catalyst.
エステル化反応においては、通常用いられているような
重合禁止剤を使用することができる。使用される重合禁
止剤としては例えばへイドロキノン、メトキシハイドロ
キノン、フェノチアジン。In the esterification reaction, commonly used polymerization inhibitors can be used. Examples of polymerization inhibitors used include hehydroquinone, methoxyhydroquinone, and phenothiazine.
ヒドロキシルアミン、フヱニレンジアミンなどが挙げら
れる。なお、反応を分子状酸素の存在下で行うと重合禁
止剤の効果を更に高めることができる。Examples include hydroxylamine and phenylenediamine. Note that the effect of the polymerization inhibitor can be further enhanced if the reaction is carried out in the presence of molecular oxygen.
このようにして得られたエステル化反応生成物はメタク
リル酸分離塔に導いて、メタクリル酸分離塔の塔頂から
メタクリル酸エステル、水および未反応アルコールを留
去させる。一方、メタクリル酸分離塔の塔底がら実質的
に全量のメタクリル酸を含む液を抜きだして循環液とし
てエステル化反応器に循環させる。The esterification reaction product thus obtained is introduced into a methacrylic acid separation column, and the methacrylic acid ester, water and unreacted alcohol are distilled off from the top of the methacrylic acid separation column. On the other hand, a liquid containing substantially the entire amount of methacrylic acid is extracted from the bottom of the methacrylic acid separation column and is circulated to the esterification reactor as a circulating liquid.
メタクリル酸分離塔においては、前述したとおり、塔底
温度が規定温度以下に納まるように完全にメタクリル酸
を分離せずにメタクリル酸エステルを含んだ状態で塔底
液を抜き出す。次いで、塔底液は循環液としてエステル
化反応器に循環するのであるが、エステル化反応を進め
るうえでは該循環液組成はメタクリル酸エステルおよび
水を減らしメタクリル酸を増やす方が有利になる。従っ
てメタクリル酸分離塔から排出される塔底液は、目的と
するエステル、反応条件によっても異なるが、メタクリ
ル酸の濃度が５０重量％以上、より好ましくは６０重量
％以上、また水の濃度が５重量％以下、より好ましくは
２重量％以下であるのが望ましい。In the methacrylic acid separation column, as described above, the bottom liquid is extracted in a state containing methacrylic ester without completely separating methacrylic acid so that the bottom temperature is below a specified temperature. Next, the bottom liquid is circulated to the esterification reactor as a circulating liquid, and in order to proceed with the esterification reaction, it is advantageous to reduce the methacrylic acid ester and water and increase the methacrylic acid in the circulating liquid composition. Therefore, the bottom liquid discharged from the methacrylic acid separation tower has a methacrylic acid concentration of 50% by weight or more, more preferably 60% by weight or more, and a water concentration of 5% by weight, although it varies depending on the target ester and reaction conditions. It is desirable that the amount is not more than 2% by weight, more preferably not more than 2% by weight.
メタクリル酸分離塔においてもエステル化反応に関して
例示し、たと同様の重合禁止剤を用いる。In the methacrylic acid separation column, the same polymerization inhibitor as exemplified for the esterification reaction is used.
分子状酸素の存在下で行うと重合禁止剤の効果を更に高
めることができることも同様である。Similarly, the effect of the polymerization inhibitor can be further enhanced if it is carried out in the presence of molecular oxygen.
メタクリル酸分離塔塔底液は循環液としてエステル化反
応器に循環されるが、その一部を薄層蒸発器に導いて重
合物などの高沸点不純物を除去するなど適宜精製処理し
た後エステル化反応器に循環させるのが好ましい。エス
テル化反応器に循環させる循環液量は多すぎても少なす
ぎてもエステル化反応に必要な樹脂量が増加するので好
ましくない。循環液量は新規供給量に対して１〜５倍量
が適切である。The bottom liquid of the methacrylic acid separation tower is circulated as a circulating liquid to the esterification reactor, but a portion of it is led to a thin layer evaporator to remove high-boiling point impurities such as polymers, and is then subjected to appropriate purification treatment before esterification. Preferably, it is recycled to the reactor. If the amount of circulating liquid circulated to the esterification reactor is too large or too small, the amount of resin required for the esterification reaction will increase, which is not preferable. The appropriate amount of circulating fluid is 1 to 5 times the new supply amount.
次に、本発明の好適な実施態様を例示する第１図に従っ
て更に詳しく説明する。Next, a preferred embodiment of the present invention will be described in more detail with reference to FIG. 1, which illustrates it.
ライン１よりメタクリル酸、ライン２よりアルコール、
ライン７より循環液を供給し、これら混合物を多孔質の
強酸性陽イオン交換樹脂を充填したエステル化反応器１
０１に供給する。エステル化反応器１０１において、反
応器入口３および出口４の液を分析してメタクリル酸の
転化率を監視し、該転化率が常に一定になる様に反応温
度を調節しながらエステル化反応を行う。Methacrylic acid from line 1, alcohol from line 2,
The esterification reactor 1 is supplied with circulating liquid from line 7 and filled with a porous strongly acidic cation exchange resin.
Supply to 01. In the esterification reactor 101, the conversion rate of methacrylic acid is monitored by analyzing the liquid at the reactor inlet 3 and outlet 4, and the esterification reaction is carried out while adjusting the reaction temperature so that the conversion rate is always constant. .
生成エステル、未反応メタクリル酸、未反応アルコール
および生成水からなるエステル化反応生成物をエステル
化反応器１０１の出口４から抜き出し、メタクリル酸分
離塔１０２に供給して蒸留する。メタクリル酸分離塔１
０２の塔底から実質的に全量の未反応メタクリル酸を含
む液を抜き出し、循環液としてライン７よりエステル化
反応器１０１へ循環する。ここでメタクリル酸分離塔塔
底液の一部を薄層蒸発器１０３に供給して重合物などの
高沸点不純物をライン６より糸外に除去し、留出物を残
りのメタクリル酸分離塔塔底液とともに循環する。An esterification reaction product consisting of the produced ester, unreacted methacrylic acid, unreacted alcohol, and produced water is extracted from the outlet 4 of the esterification reactor 101, supplied to the methacrylic acid separation column 102, and distilled. Methacrylic acid separation column 1
A liquid containing substantially the entire amount of unreacted methacrylic acid is extracted from the bottom of the column 02 and is circulated to the esterification reactor 101 via line 7 as a circulating liquid. Here, a part of the bottom liquid of the methacrylic acid separation column is supplied to the thin layer evaporator 103 to remove high boiling point impurities such as polymers from the line 6, and the distillate is transferred to the bottom of the methacrylic acid separation column. It circulates with the liquid.
また、メタクリル酸分離塔１０２の塔頂からは生成エス
テル、未反応アルコールおよび生成水が留出し、受器１
０４にてエステル相と水相とに二相分離する。一部は還
流液としてメタクリル酸分離塔１０２に循環する。ライ
ン８よりエステル相を抜き出し、図外の精製工程に送っ
てメタクリル酸エステル製品を得る。一方、ライン９よ
り水相を抜き出し、図外のアルコール回収工程または廃
水処理工程に送る。Furthermore, produced ester, unreacted alcohol, and produced water are distilled from the top of the methacrylic acid separation column 102, and the receiver 1
At 04, the two phases are separated into an ester phase and an aqueous phase. A portion is recycled to the methacrylic acid separation column 102 as a reflux liquid. The ester phase is extracted from line 8 and sent to a purification process not shown in the figure to obtain a methacrylic acid ester product. On the other hand, the aqueous phase is extracted from line 9 and sent to an alcohol recovery process or a wastewater treatment process (not shown).
本発明においては、エステル化反応はメタクリル酸の転
化率が常に一定になる様に行なわれるので、エステル化
反応生成物の組成は安定しており、メタクリル酸分離塔
１０２の運転条件も安定して行なわれる。即ち、メタク
リル酸分離塔１０２の操作温度は一定し、塔底から抜き
出きべ 反応器に循環される循環液の組成も一定してい
る。In the present invention, the esterification reaction is carried out so that the conversion rate of methacrylic acid is always constant, so the composition of the esterification reaction product is stable and the operating conditions of the methacrylic acid separation column 102 are also stable. It is done. That is, the operating temperature of the methacrylic acid separation column 102 is constant, and the composition of the circulating liquid to be withdrawn from the bottom of the column and circulated to the reactor is also constant.
［実施例］ 更に、本発明を以下の実施例によって詳しく説明する。[Example] Further, the present invention will be explained in detail by the following examples.
なお、各実施例は第１図の装置を用いて行ない、メタク
リル酸の転化率は反応器入口液、出口液のメタクリル酸
濃度を分析して下記式に従って計算した。Each Example was carried out using the apparatus shown in FIG. 1, and the conversion rate of methacrylic acid was calculated according to the following formula by analyzing the methacrylic acid concentration of the reactor inlet liquid and outlet liquid.
メタクリル酸の転化率＝
第１表
第１図の装置を用い、純度９９．７重量％のメタクリル
酸およびメタノールを原料とし、エステル化反応器に多
孔質の陽イオン交換樹脂５５１！を充填してメタクリル
酸メチルの製造を行なった。Conversion rate of methacrylic acid = Using the apparatus shown in Table 1 and Figure 1, methacrylic acid and methanol with a purity of 99.7% by weight are used as raw materials, and porous cation exchange resin 551! is placed in an esterification reactor. was charged to produce methyl methacrylate.
運転を開始して定常状態に達してから７ケ月間連続運転
を行なった。運転中、反応器でのメタクリル酸の転化率
を一定に保つ為に樹脂の経時劣化に伴い反応温度を徐々
に上昇させた結果、７ケ月間の連続運転後反応温度は８
９℃となったがこの間の反応温度の上昇割合はほぼ一定
であった。メタクリル酸の転化率、エステル化反応生成
物の組成、メタクリル酸分離塔の塔底温度、循環液の組
成などは安定していた。平均的な値を第１表に示した。After starting the operation and reaching a steady state, continuous operation was performed for 7 months. During operation, in order to keep the conversion rate of methacrylic acid in the reactor constant, the reaction temperature was gradually increased as the resin deteriorated over time. As a result, the reaction temperature after 7 months of continuous operation was 8.
Although the temperature reached 9°C, the rate of increase in the reaction temperature during this period was almost constant. The conversion rate of methacrylic acid, the composition of the esterification reaction product, the bottom temperature of the methacrylic acid separation column, the composition of the circulating liquid, etc. were stable. The average values are shown in Table 1.
医較舅１
運転中の反応温度を８９℃に保った他は実施例１と同様
にしてメタクリル酸メチルの製造を実施した。その結果
、樹脂の経時劣化が起こり、メタクリル酸の転化率は徐
々に低下し、メタクリル酸分離塔の塔底温度は徐々に上
昇して５ケ月間で連続運転を停止せざるをえなかった。Medical Comparison 1 Methyl methacrylate was produced in the same manner as in Example 1, except that the reaction temperature during operation was maintained at 89°C. As a result, the resin deteriorated over time, the conversion rate of methacrylic acid gradually decreased, and the bottom temperature of the methacrylic acid separation column gradually increased, necessitating the suspension of continuous operation after 5 months.
運転を開始して定常状態に達したときのメタクリル酸の
転化率は４１．８％であったのが運転停止時には２２゜
５％に低下しており、実施例１に比べて樹脂寿命は明ら
かに短くなっており、単位触媒量当りの総生産量も少な
かった。The conversion rate of methacrylic acid was 41.8% when the operation started and a steady state was reached, but it decreased to 22.5% when the operation was stopped, and the resin life is clearly longer than in Example 1. The total production amount per unit amount of catalyst was also small.
爽胤且ユ
実施例１と同じ純度９９．７１景％のメタクリル酸とブ
タノールとを原料とし、エステル反応器に多孔質の陽イ
オン交換樹脂２０Ｑを充填し、反応温度７５℃にて実施
例１に準じてメタクリル酸ブチルの製造を開始した。Using methacrylic acid and butanol with a purity of 99.71% as in Example 1 as raw materials, the ester reactor was filled with porous cation exchange resin 20Q, and the reaction temperature was 75°C. The production of butyl methacrylate was started in accordance with the above.
運転を開始して定常状態に達したとき、各流量はメタク
リル酸（ライン１）１．３３ｋｇ／時、ブタノール（ラ
イン２）１．４９ｋｇ／時、Ｖｉ環液（ライン？）５．
６４ｋｇ／時、メタクリル酸の転化率は２８．５％、メ
タクリル酸分離塔塔底温度は１００℃であった。When the operation started and a steady state was reached, each flow rate was 1.33 kg/hour for methacrylic acid (line 1), 1.49 kg/hour for butanol (line 2), and 5.
64 kg/hour, the conversion rate of methacrylic acid was 28.5%, and the bottom temperature of the methacrylic acid separation column was 100°C.
７ケ月間連続運転する間にエステル化反応温度は７５℃
からほぼ一定の割合で上昇し、８６℃になった。しかし
、７ケ月間の連続運転中、メタクリル酸の転化敦 エス
テル化反応生成物の組成、メタクリル酸分離塔の塔底温
度、循環液の組成などは安定していた。The esterification reaction temperature was 75℃ during continuous operation for 7 months.
The temperature rose at an almost constant rate from then on to 86°C. However, during seven months of continuous operation, the composition of the methacrylic acid conversion and esterification reaction product, the bottom temperature of the methacrylic acid separation column, and the composition of the circulating fluid remained stable.
［発明の効果］
本発明によればメタクリル酸の転化率が常に一定になる
様にエステル化反応させるので、メタクリル酸分離塔の
運転条件も安定しており、メタクリル酸分離塔での塔底
温度上昇による重合物の増加もなく、またメタクリル酸
分離塔塔底液の組成も一定するので反応器の液組成も一
定であり、その結果樹脂のｌｌ１ｉｔＸ１． 収縮９
割れなどの問題を防いで樹脂寿命を長く維持することが
でき、前記本発明の目的が達成される。本発明において
は、反応器の温度が規定の温度に達した時点をもって触
媒の寿命とし、触媒交換を行なう。本発明によれば、新
たに充填された触媒が寿命に到達したとして交換される
までの単位触媒量当りの総生産量は前記従来の方法に比
べて多い値が得られる。[Effects of the Invention] According to the present invention, since the esterification reaction is carried out so that the conversion rate of methacrylic acid is always constant, the operating conditions of the methacrylic acid separation column are also stable, and the bottom temperature of the methacrylic acid separation column is kept constant. There is no increase in polymerized products due to the rise, and the composition of the bottom liquid of the methacrylic acid separation column is also constant, so the liquid composition of the reactor is also constant, and as a result, the ll1itX1. contraction 9
Problems such as cracking can be prevented and the life of the resin can be maintained for a long time, thus achieving the object of the present invention. In the present invention, the life of the catalyst is reached when the temperature of the reactor reaches a specified temperature, and the catalyst is replaced. According to the present invention, the total production amount per unit amount of catalyst until the newly filled catalyst reaches the end of its life and is replaced can be increased compared to the conventional method.
第１図は本発明の好適な実施態様を例示するフローシー
ト図を表わす。
１０１・・・エステル化反応器
１０２・・・メタクリル酸分離塔
１０３・・・薄層蒸発器
１０４・・・受器
１・・・メタクリル酸供給ライン
２・・・アルコール供給ライン
３・・・エステル化反応器入口
４・・・エステル化反応器出口
５・・・メタクリル酸分離塔塔底液抜き出しライン６・
・・高沸点物抜き出しライン
７・・・循環液供給ライン
８・・・エステル相抜き出しライン
９・・・水相抜き出しラインFIG. 1 depicts a flow sheet diagram illustrating a preferred embodiment of the invention. 101... Esterification reactor 102... Methacrylic acid separation column 103... Thin layer evaporator 104... Receiver 1... Methacrylic acid supply line 2... Alcohol supply line 3... Ester Esterification reactor inlet 4... Esterification reactor outlet 5... Methacrylic acid separation column bottom liquid extraction line 6.
...High boiling point extraction line 7...Circulating liquid supply line 8...Ester phase extraction line 9...Aqueous phase extraction line
Claims (2)
コールまたは脂環式アルコールとをエステル化反応器に
供給し、該反応器にて強酸性陽イオン交換樹脂を触媒と
してメタクリル酸の転化率が常に一定になる様に反応温
度を調節しながらエステル化反応させ、得られた反応生
成物をメタクリル酸分離塔に導いて、メタクリル酸分離
塔の塔頂からメタクリル酸エステル、水および未反応ア
ルコールを留去させる一方、メタクリル酸分離塔の塔底
から実質的に全量のメタクリル酸を含む液を抜きだして
循環液としてエステル化反応器に循環させることを特徴
とするメタクリル酸エステルの製造方法。(1) Methacrylic acid and a lower aliphatic alcohol or alicyclic alcohol having 1 to 4 carbon atoms are supplied to an esterification reactor, and the methacrylic acid is converted in the reactor using a strongly acidic cation exchange resin as a catalyst. The esterification reaction is carried out while adjusting the reaction temperature so that the reaction rate is always constant, and the obtained reaction product is led to a methacrylic acid separation column, and the methacrylic acid ester, water and unreacted are separated from the top of the methacrylic acid separation column. A method for producing methacrylic acid ester, which comprises distilling off alcohol while extracting a liquid containing substantially the entire amount of methacrylic acid from the bottom of a methacrylic acid separation column and circulating it as a circulating liquid to an esterification reactor. .
、水の濃度が５重量％以下であり、かつエステル化反応
器に新規に供給される原料液の量に対する循環液の量が
１〜５倍量である請求項（１）に記載の方法。(2) The concentration of methacrylic acid in the circulating liquid is 50% by weight or more, the concentration of water is 5% by weight or less, and the amount of circulating liquid is 1% relative to the amount of raw material liquid newly supplied to the esterification reactor. The method according to claim 1, wherein the amount is ~5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1100167A JPH0686405B2 (en) | 1989-04-21 | 1989-04-21 | Method for producing methacrylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1100167A JPH0686405B2 (en) | 1989-04-21 | 1989-04-21 | Method for producing methacrylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02279654A true JPH02279654A (en) | 1990-11-15 |
| JPH0686405B2 JPH0686405B2 (en) | 1994-11-02 |
Family
ID=14266761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1100167A Expired - Lifetime JPH0686405B2 (en) | 1989-04-21 | 1989-04-21 | Method for producing methacrylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686405B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007284406A (en) * | 2006-04-20 | 2007-11-01 | Mitsui Chemicals Inc | Production method for thiol compound |
| JP2009001510A (en) * | 2007-06-19 | 2009-01-08 | Nippon Shokubai Co Ltd | Production method of (meth)acrylic ester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49126607A (en) * | 1971-09-24 | 1974-12-04 | ||
| JPS58159442A (en) * | 1982-03-17 | 1983-09-21 | Nippon Kayaku Co Ltd | Preparation of acrylic or methacrylic ester |
| JPS5912102A (en) * | 1982-07-12 | 1984-01-21 | Toshiba Corp | Labyrinth packing |
| JPS6320415A (en) * | 1986-07-12 | 1988-01-28 | Nippon Steel Corp | Method for controlling combustion of side burner of continuous heating furnace |
-
1989
- 1989-04-21 JP JP1100167A patent/JPH0686405B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49126607A (en) * | 1971-09-24 | 1974-12-04 | ||
| JPS58159442A (en) * | 1982-03-17 | 1983-09-21 | Nippon Kayaku Co Ltd | Preparation of acrylic or methacrylic ester |
| JPS5912102A (en) * | 1982-07-12 | 1984-01-21 | Toshiba Corp | Labyrinth packing |
| JPS6320415A (en) * | 1986-07-12 | 1988-01-28 | Nippon Steel Corp | Method for controlling combustion of side burner of continuous heating furnace |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007284406A (en) * | 2006-04-20 | 2007-11-01 | Mitsui Chemicals Inc | Production method for thiol compound |
| JP2009001510A (en) * | 2007-06-19 | 2009-01-08 | Nippon Shokubai Co Ltd | Production method of (meth)acrylic ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0686405B2 (en) | 1994-11-02 |
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